Aryl dechlorination and defluorination with an organic super-photoreductant

Abstract

Photoexcitation of tetrakis(dimethylamino)ethylene (TDAE) provides an exceptionally strong stoichiometric reductant, able to perform very demanding dehalogenations.

Sensitization-initiated electron transfer via upconversion: mechanism and photocatalytic applications

“…This permits convenient determination of yields and conversions by 19 F-NMR spectroscopy. 65,66 The reaction conditions were optimized with substrate 1 present at 30 mM concentration in de-aerated DMF at room temperature (Table 2). When using 1 mol% fac-[Ir(ppy) 3 ], 5 mol% of tBu Py, and 5 equivalents of DMA, a hydrodechlorination product (1-P) yield of 79% was determined aer 16 hours of irradiation (with a conversion of 96%, entry 1 in Table 2).…”

Photochemical transformation of chlorobenzenes and white phosphorus into arylphosphines and phosphonium salts

“…To validate their intermediacy, the photochemical phenylation was also analyzed starting from the different arylated Fig. 2 Reducing power of ground-state and exited-state organic photoreductant TDAE 20 and reduction potentials of used solvents (acetone and benzene), 23,24 aryl halides (fluoro-, chloro-, 21 bromo-and iodobenzene) 25 and the corresponding aryl radical. 26 Fig.…”

Metal‐Free Photoredox‐Catalyzed Hydrodefluorination of Fluoroarenes Utilizing Amide Solvent as Reductant

“…Concerning reduction of fluoroarenes, photoredox‐catalyzed partial HDF reactions and C−F functionalizations of polyfluoroarenes have been reported (Scheme 1b) [10] . However, HDF of monofluoroarene derivatives with photoredox systems remains undeveloped due to their inertness towards single‐electron‐transfer (SET), [11] while several methods utilizing photoirradiation have recently been developed, which involve direct photoexcitation of fluoroarenes [12a,b] and the use of stoichiometric amounts of strong photoreductants [12c,d] …”